JP4896886B2 - Radiation curable coating composition - Google Patents

Description

  The present invention relates to radiation curable coating compositions containing NIR-photoinitiators, new formulations of NIR-photoinitiators and uses thereof.

  EP 408322 describes a one-component photoinitiator in the form of a salt from a cyanine dye and a specific borate ion.

  Similarly, one-component photoinitiator systems are known in which a cyanine-, xanthylium- or thiazine dye as cation and a borate compound as anion are used (see, for example, EP-A 223587).

  All these systems known from the state of the art are common in that they exhibit a rather low solubility in the paint, where they cause defects in the coating, especially when they precipitate as crystals.

  This invention relates to a two-component NIR-photoinitiator system comprising at least one sensitizing dye (also referred to as sensitizer) and at least one radical polymerization initiator (also referred to as co-initiator). Is described.

  As sensitizing dyes, dyes, in particular cyanine-, xanthylium- or thiazine dyes are frequently used in the state of the art, and co-initiators include, for example, borate salts, sulfonium salts, iodonium salts, sulfones. Peroxides, pyridine-N-oxides or halogenmethyltriazines are used.

  Cyanine dyes consist of a cyanine-cation and a corresponding anion. Here, this may be a separate anion or an internal anion, ie the anion group may be chemically bonded to the cyanine-cation. Usually they occur during their manufacture as simple salts, for example as halogenides, tetrafluoroborate, perchlorate or tosylate. No cyanine dye having an anion containing a long-chain alkyl group or an alkyl-substituted aryl group has been conventionally known. Cyanine dyes are commercially available.

  Cyanine dyes are often used as alkyl- and aryl-sulfonates, sulfates, chlorides or the like, as is known, for example, from US Pat. No. 6,014,930 or EP-A 342576.

  From DE-A 19730498 and DE-A 19648256 are known compositions which are prepared from separated salts and borate salts of cationic dyes and which can also be used in admixture with UV-photoinitiators.

  The specification of the German patent application with the file number 102004011347.5 shows a minimum solubility of 0.1% by weight in the printing ink and binds a substituent on the central boron atom as a counter ion via four oxygen atoms A cyanine dye as a NIR-absorber for laser radiation, which may have a borate as described above. However, such borates are photochemically inactive and cannot function as photoinitiators.

  The object of the present invention was to provide a NIR-photoinitiator system which on the one hand has good solubility and on the other hand has a good photoactivation capability with NIR-rays.

［式中、ｎは１又は２であり、基Ｒ^１〜Ｒ^９は次のものを表す：
− Ｒ^１及びＲ^２は相互に無関係に、Ｃ−原子数１〜２０を有する線状の又は分枝した、
置換又は非置換のアルキル−又はアラルキル基、
− Ｒ^３及びＲ^４は相互に無関係に、Ｈ、ＣＦ_３又はＣＮ、
− Ｒ^５及Ｒ^６は相互に無関係に、群 −Ｈ、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−ＮＯ_２、
−ＣＮ、−ＣＦ_３、−ＳＯ_２ＣＦ_３、−Ｒ^１、−ＯＲ^１、アリール−又は−Ｏ−ア
リールから選択される同種又は異種の置換基１個以上、
− Ｒ^７は、−Ｈ、−Ｃｌ、−Ｂｒ、−Ｉ、−フェニル、−Ｏ−フェニル、−Ｓ−フェニ
ル、−Ｎ（フェニル）_２、−ピリジル、バルビツール酸−又はジメドン基、ここで、
フェニル基は、なお更に置換されていてもよい、
− Ｒ^８及びＲ^９は相互に無関係に、＞Ｃ（ＣＨ_３）_２、−Ｏ−、−Ｓ−、＞ＮＲ^１又は
−ＣＨ＝Ｃ− ］を有し、
かつ、この際、アニオンＡｎ^ｍ−は、極性のイオン性ヘッド基Ａ １個並びに非極性基
Ｒ^１０ ｋ個を有する、一般式 ［ＡＲ^１０ _ｋ］^ｍ−
［ｋは、１、２又は３の数であり、ｍは１又は２であり、かつ
非極性基Ｒ^１０は相互に無関係に、次の群：
− Ｃ−原子数６〜３０を有する、線状の、分枝した又は環状のアルキル基並びに
− 一般式 −アリール−Ｒ^１１のアルキルアリール基
から選択され、ここで、Ｒ^１１はＣ−原子数３〜３０を有する、線状の又は分枝したアルキル基である］を有するか、
又はアニオンＡｎ^ｍ−は、一般式（Ｖ）又は（ＶＩ）：

［式中、Ｒ^１０は前記と同様に定義され、Ｒ^１２は、Ｈ又はＣ−原子数１〜２０を有する、線状の、環状の又は分枝したアルキル基の群から選択される少なくとも１個の置換基であり、かつ
この際、基Ｒ^１０、Ｒ^１１及びＲ^１２中で隣接していないＣ−原子は、場合によりＯ−原子で置換されていてもよく、かつ／又は基Ｒ^１０、Ｒ^１１及びＲ^１２は全て又は部分的に、基の非極性が実質的に影響されないことを条件として、弗素化されていてよい］のボレート−アニオンである｝少なくとも１種及び
（Ｂ）１個の会合した対イオン１／ｘ Ｋａｔ^ｘ＋を有する、式（ＶＩＩ）：

［式中、ｘは１又は２であり、Ｋａｔはカチオンであり、
ｚ^１、ｚ^２、ｚ^３及びｚ^４は相互に無関係に、それぞれ０又は１であり、
この際、ｚ^１＋ｚ^２＋ｚ^３＋ｚ^４の合計は０、１、２又は３、好ましくは０、１又は２、特に好ましくは０又は１、全く特別好ましくは０であり、
Ｙ^１、Ｙ^２、Ｙ^３及びＹ^４は相互に無関係に、それぞれ、Ｏ、Ｓ又はＮＲ^１７であり、
Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６はそれぞれ相互に無関係に、Ｃ_１〜Ｃ_１８−アルキル、場合により１個以上の酸素−及び／又は硫黄原子によって及び／又は１個以上の置換又は非置換のイミノ基によって中断されたＣ_２〜Ｃ_１８−アルキル、Ｃ_６〜Ｃ_１２−アリール、Ｃ_５〜Ｃ_１２−シクロアルキル基であるか又は酸素−、窒素−及び／又は硫黄原子を有する５〜６員のヘテロ環であり、ここで、記載の基はそれぞれ、アリール、アルキル、アリールオキシ、アルキルオキシ、ヘテロ原子及び／又はヘテロ環で置換されていてよく、かつ
Ｒ^１７は、水素、Ｃ_１〜Ｃ_１８−アルキル又はＣ_６〜Ｃ_１２−アリールを表す、
但し、基Ｒ^１３〜Ｒ^１６の少なくとも１つはＣ_１〜Ｃ_１８−アルキル基であり、基Ｒ^１３〜Ｒ^１６の少なくとも１つはＣ_６〜Ｃ_１２−アリール基であり、この際、記載の基は、それぞれアリール、アルキル、アリールオキシ、アルキルオキシ、ヘテロ原子及び／又はヘテロ環で置換されていてよいことを条件とする］の共−開始剤少なくとも１種
を含有する混合物によって解決された。 This task consists of the following ingredients:
(A) Absorbent composed of one cyanine-cation Cya ^{+ and} one corresponding anion 1 / m An ^m- 1 {in this case, the cyanine-cation is represented by the general formulas (I), (II), ( III) or (IV):

[Wherein n is 1 or 2 and groups R ^{1 to} R ⁹ represent the following:
R ¹ and R ² are, independently of one another, linear or branched having 1 to 20 C atoms.
A substituted or unsubstituted alkyl- or aralkyl group,
R ³ and R ⁴ are independently of each other H, CF ₃ or CN,
R ⁵ and R ⁶ are independently of each other the groups -H, -F, -Cl, -Br, -I, -NO ₂ ,
One or more of the same or different substituents selected from —CN, —CF ₃ , —SO ₂ CF ₃ , —R ¹ , —OR ¹ , aryl- or —O-aryl,
- R ⁷ is, -H, -Cl, -Br, -I, - phenyl, -O- phenyl, -S- phenyl-, -N _{(phenyl) 2,} - pyridyl, barbituric acid - or dimedone radical, where so,
The phenyl group may be further substituted,
- R ⁸ and ^{R 9} independently of one _{another,> C (CH 3) 2} , -O -, - S -,> NR 1 or have a -CH = C-],
And, this time, the anion ^{An m-is} one ionic head group of polar A as well as a non-polar group ^{R 10} k pieces, the general formula ^[AR ₁₀ ^{k] m-}
[K is a number of 1, 2 or 3; m is 1 or 2; and the nonpolar group R ¹⁰ is independent of the following group:
- C- atoms having a number 6 to 30, linear, alkyl group branched or cyclic and - formula - is selected from alkyl aryl group of ^{-R 11, wherein, R 11} is the number of C- atoms A linear or branched alkyl group having 3 to 30],
Or the anion An ^m- is represented by the general formula (V) or (VI):

Wherein R ¹⁰ is as defined above, and R ¹² is at least one selected from the group of linear, cyclic or branched alkyl groups having 1 to 20 H or C atoms. C-atoms that are non-adjacent in the radicals R ¹⁰ , R ¹¹ and R ¹² may optionally be substituted with O-atoms and / or the radical R ^10. R ¹¹ and R ¹² are all or partly fluorinated borate-anions provided that the non-polarity of the group is substantially unaffected} at least one and (B) 1 Having the associated counterion 1 / x Kat ^{x +} , formula (VII):

[Wherein x is 1 or 2, Kat is a cation,
z ¹ , z ² , z ³ and z ⁴ are each independently 0 or 1,
In this case, the sum of z ¹ + z ² + z ³ + z ⁴ is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1, very particularly preferably 0,
Y ¹ , Y ² , Y ³ and Y ⁴ are independently of each other O, S or NR ¹⁷ ;
R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently of _one another C ₁ -C ₁₈ -alkyl, optionally with one or more oxygen- and / or sulfur atoms and / or with one or more substituted or non-substituted interrupted by an imino group substituted _C 2 _{-C 18} - _alkyl, C 6 _{-C 12} - _aryl, C 5 _{-C 12} - or a cycloalkyl group or an oxygen - nitrogen - 5 with and / or sulfur atoms A 6-membered heterocycle, wherein each of the described groups may be substituted with an aryl, alkyl, aryloxy, alkyloxy, heteroatom and / or heterocycle, and R ¹⁷ is hydrogen, C Represents ₁ -C ₁₈ -alkyl or C ₆ -C ₁₂ -aryl,
Provided that at least one of the groups R ^{13 to} R ¹⁶ is a C _{1 to} C ₁₈ -alkyl group, and at least one of the groups R ^{13 to} R ¹⁶ is a C _{6 to} C ₁₂ -aryl group. The groups of have been solved by a mixture containing at least one co-initiator, provided that each group can be substituted with aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles .

In this case, C ₁ -C ₁₈ -alkyl optionally substituted with aryl, alkyl, aryloxy, alkyloxy, heteroatom and / or heterocycle is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, s- Butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p -Chlorobenzyl, 2,4-dichlorobenzyl, p-methoxyben M, ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di (methoxycarbonyl) -ethyl, 2-methoxyethyl 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolane-2 -Yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1, 1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl , Butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6- Hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylamino Butyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2 -Phenoxyethyl, 2-phenoxypropyl, 3- Enoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxy Represents propyl, 4-ethoxybutyl or 6-ethoxyhexyl;
C ₂ -C ₁₈ -alkyl optionally interrupted by one or more oxygen- and / or sulfur atoms and / or by one or more substituted or unsubstituted imino groups is, for example, 5-hydroxy-3-oxa- Pentyl, 8-hydroxy-3,6-dioxa-octyl, 11-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-oxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy- 3,6-dioxa-octyl, 11-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxy Saheptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-oxa- Tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11- Represents ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-dioxa-tetradecyl.

  The number of oxygen- and / or sulfur atoms and / or imino groups is not limited. Usually they do not exceed 5 in the group, preferably do not exceed 4, and particularly preferably do not exceed 3.

  In addition, there are usually at least 1, preferably at least 2 carbon atoms between the two heteroatoms.

  Substituted and unsubstituted imino groups may be, for example, imino-, methylimino-, iso-propylimino, n-butylimino- or t-butylimino groups.

Furthermore,
C ₆ -C ₁₂ -aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatom and / or heterocycle is, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl. , Chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, t-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxy Phenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphene 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethyl Represents phenyl,
Optionally aryl, alkyl, aryloxy, alkyloxy, C ₅ -C 12 substituted with heteroatoms and / or heterocycles _- cycloalkyl, such as cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, Represents methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and saturated or unsaturated bicyclic systems and for example norbornyl or norbornenyl And a 5- to 6-membered heterocycle having an oxygen-, nitrogen- and / or sulfur atom, for example Ryl, thiophenyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or t -Represents butylthiophenyl.

Y ¹ , Y ² , Y ³ and Y ⁴ are independently of each other preferably oxygen or NR ¹⁷ , particularly preferably oxygen.

R ¹⁷ is preferably oxygen or C ₁ -C ₄ -alkyl.

C ₁ -C ₄ -alkyl in the present invention is methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl or t-butyl, preferably methyl, ethyl or n-butyl, particularly preferably methyl or ethyl, Special preference is given to methyl.

R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are independently of each other C ₁ -C ₁₈ -alkyl, C ₆ -C ₁₂ -aryl or C ₅ -C ₁₂ -cycloalkyl, more preferably C ₁ -C. ₁₈ - alkyl and _C 6 _{-C 12} - aryl, very particularly preferably the group: methyl, ethyl, propyl, isopropyl, n- butyl, s- butyl, t- butyl, pentyl, hexyl, heptyl, octyl, 2- Ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1 -Phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethi 1- (p-butylphenyl) -ethyl, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, selected from the group of t-butylphenyl and dodecylphenyl, in particular methyl, ethyl, propyl, n-butyl, hexyl, octyl, 2-ethylhexyl, dodecyl, benzyl, 2-phenylethyl, phenyl, tolyl, α-naphthyl and Selected from the group of β-naphthyl and in particular selected from the group of methyl, ethyl, n-propyl, n-butyl, benzyl, phenyl and tolyl.

According to the invention, at least one of the groups R ^{13 to} R ¹⁶ is C ₁ -C ₁₈ -alkyl, at least one is C ₆ -C ₁₂ -aryl, preferably at least one is C _{1 to} C ₁₈ -alkyl, at least one is C _{6 to} C ₁₂ -aryl and the other two are from the group including C ₁ -C ₁₈ -alkyl and C ₆ -C ₁₂ -aryl as well. is selected, particularly preferably at least one is _C 1 _{-C 18} - alkyl and at least two are _C 6 _{-C 12} - aryl, and very particularly preferably, one is _C 1 _{-C 18} - is alkyl , three in _C 6 _{-C 12} - aryl.

  The amount of sensitizing dye contained in the coating composition according to the invention is selected by the person skilled in the art so that sufficient photocuring of the composition is achieved. In normal cases, an amount of less than 5% by weight is sufficient. In particular, an amount of 0.05 to 4% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.2 to 2.5% by weight, very particularly preferably, based on the total of all components of the coating composition. An amount of 0.3 to 2.0% by mass was effective. According to the invention, it should be ensured that the sensitizing dye to be added is completely dissolved in the coating composition.

  The solubility of the sensitizing dye in the coating composition is advantageously at least 0.2% by weight, particularly preferably at least 0.5% by weight, very particularly preferably at least 1.0% by weight, for example at least 2% by weight. It is.

In the present invention, the sensitizing dye is composed of one cyanine-cation Cya ^{+ and} one corresponding anion 1 / m An ^m- (where m may be a value of 1 or 2 in particular). It is an absorbent.

The cyanine-cations according to the invention have the general formula selected from the following formulas (I) to (IV):

Here, n is 1 or 2, and the groups R ^{1 to} R ⁹ represent the following:
R ¹ and R ² independently of one another represent a linear or branched alkyl- or aralkyl group having 1 to 20 carbon atoms. Examples include methyl-, ethyl-, 1-propyl-, 2-propyl-, 1-butyl-, 2-butyl-, t-butyl-, 1-pentyl-, 1-hexyl-, 2-ethyl-1. -Hexyl-, 1-octyl-, 1-decyl- or 1-dodecyl groups are included. This is especially the case for linear alkyl groups. The group is preferably a methyl-, ethyl-, 1-butyl- or 1-dodecyl group. As is known in principle, an aralkyl group is an alkyl group substituted with an aryl group. Examples include benzyl- or phenylethyl groups. R ¹ and R ² may be similar or different from each other. R ¹ and R ² are preferably the same group.

R ¹ and R ² may optionally be further substituted. Mention may be made here in particular of functional groups, for example amino- or hydroxy groups. If present, this may in particular be a functional group present at the end of the alkyl group.

R ³ and R ⁴ are independently of each other —H, —CF ₃ or —CN. R ³ and R ⁴ are preferably the same group.

The groups R ⁵ and R ⁶ are different or preferably selected from the group of —H, —F, —Cl, —Br, —I, —NO ₂ , —CN, —CF ₃ or —SO ₂ CF _3. Is a group of the same kind. R ⁵ and R ⁶ may be a group —R ¹ or —OR ¹ , where R ¹ represents each of the foregoing. Furthermore, this may be an aryl- or -O-aryl- group, where aryl is preferably phenyl. R ⁵ and R ⁶ are advantageously —H, —Cl, —Br or —I or an alkyl group. Each terminal ring can have a plurality of the same or different substituents R ⁵ or R ⁶ on different positions of the ring. Preferably, there are advantageously less than two substituents in each ring, particularly preferably only one each.

R ⁷ may be -H, -Cl, -Br, -I, -phenyl, -O-phenyl, -S-phenyl, -N (phenyl) ₂ , -pyridyl, barbituric acid- or a dimedone group. In this case, the phenyl group may still be further substituted. Further substituents, for example linear or branched alkyl groups such as methyl - or ethyl group, or _{-F, -Cl, -Br, -I,} -NO 2, even -CN or -CF ₃ Good.

The groups R ⁸ and R ⁹ are different or preferably the same group selected from the group> C (CH ₃ ) ₂ , —O—, —S—,> NR ¹ or —CH═CH—. > C (CH ₃ ) ₂ is particularly preferred.

The counter ion An ^m− for the cyanine cation can have the general formula [AR ¹⁰ _k ] ^m− . This includes at least one polar ionic head group A as well as k non-polar groups R ¹⁰ , where k is a number 1, 2 or 3 and m is 1 or 2. Anion preferably has a group R ¹⁰ of only one. Furthermore, this is preferably a monovalent anion. If a plurality of nonpolar groups R ¹⁰ are present in the anion, these may be different or advantageously the same. Of course, this may be a mixture of different anions.

The group R ¹⁰ may be a linear, branched or cyclic alkyl group having 6 to 30 carbon atoms. The alkyl group R ¹⁰ advantageously has 6 to 12 carbon atoms. Examples of suitable groups include 1-hexyl-, cyclohexyl-, 2-ethyl-1-hexyl-, 1-octyl-, 1-nonyl-, 1-decyl-, 1-undecyl-, 1-dodecyl- or A 1-tetradecyl group is included. A linear alkyl group is preferred.

Furthermore this is the general formula - aryl -R 11 ^(wherein, R ¹¹ is a is a linear or branched alkyl group having C- atoms 3-30) may be an alkyl aryl group. Examples of suitable groups are 1-propyl-, 2-propyl-, 1-butyl-, 2-butyl-, t-butyl-, 1-pentyl-, 1-hexyl-, cyclohexyl-, 2-ethyl- 1-hexyl-, 1-octyl-, 1-nonyl-, 1-decyl-, 1-undecyl-, 1-dodecyl- or 1-tetradecyl groups are included. The alkyl radical R ¹¹ advantageously has 6 to 12 carbon atoms. Linear alkyl groups are particularly preferred.

  An aryl unit is a group resulting from the formal abstraction of a significant number of hydrogen atoms from an aromatic hydrocarbon, preferably benzene or naphthalene.

The aryl unit is in particular a phenylene group, preferably a 1,4-phenylene group. Suitable alkyl aryl _{group, - (C 6 H 4)} -C 3 H 7, - (C 6 H 4) -C 6 H 13 or _{- (C 6 H 4) -C} 12 H 25 and the like .

The polar ionic head group A is in particular an anion of a 1- or divalent acid group. This may be any inorganic or organic acid group. Preference is given to carboxyl groups or S-, P- and / or B-containing acid groups. This is for example the _{^{group: -SO 3 -, -OSO 3 -}} , -COO - a group selected from the group of _{^{-, -PO 3 2-, -OPO 3}} 2- or (-O) PO ₂ Good.

  Examples of particularly suitable anions are alkyl sulfonates having an alkyl group, in particular a linear alkyl group having 6 to 12 carbon atoms, such as n-octyl sulfonate, n-decyl sulfonate or n-dodecyl sulfonate and C-atoms. Examples include 4-alkylbenzene sulfonate having an alkyl group of 6 to 12, such as 4-hexylbenzene sulfonate, 4-octylbenzene sulfonate, 4-decylbenzene sulfonate, or 4-dodecylbenzene sulfonate. Here, as is known in principle, this may be an industrial product having a distribution of various alkyl groups of different lengths.

のボレート−アニオンであってもよい。 The counter anion An ^m- for the cyanine cation is represented by the general formula (V) or (VI):

Or a borate-anion.

R ¹⁰ is a group as defined above. There may be one or two identical or different substituents for each of the chelating ligands. Advantageously, there is one substituent each. R ¹² is each one or more of the same or different substituents selected from the group of linear, cyclic or branched alkyl groups having 1 to 20 H or C atoms, preferably C-atoms It is group which has number 2-12. Advantageously, only one alkyl group is present as a substituent. Such borate-anions are obtained, for example, from boric acid and the corresponding dialcohol.

In the group R ¹⁰ , R ¹¹ or R ¹² , the non-adjacent C-atom may optionally be substituted with an O-atom and / or the group R ¹⁰ , R ¹¹ or R ¹² is It may be fully or partially fluorinated provided that the nonpolarity is not substantially changed thereby. In one preferred embodiment, these groups are not fluorinated.

  Production of the sensitizing dye according to the present invention can be carried out using various methods. This can be produced, for example, using a two-step process, in which the first step synthesizes a cyanine cation with the usual anions such as iodide, tetrafluoroborate, perchlorate or paratoluenesulfonate. Manufacturing recipes are known to those skilled in the art. Examples include DE-A 3721850, EP-A 627660 and the literature cited therein. Cyanine-based sensitizing dyes are also available on the market.

In the second step, the normal anion is then exchanged with the anion An ^m- according to the invention using a suitable method.

This can be done, for example, by charging the starting material together with the corresponding acid H _m An into an organic solvent that is not miscible with water, in which case the absorbent should be insoluble therein. be able to. In particular, a non-volatile organic solvent having a specific polarity is suitable. This may for example be dichloromethane. Subsequently, the organic solution or suspension is extracted with water until the initial anion is completely removed from the organic solution. The sensitizing dye according to the invention can be obtained by removing the solvent from the solution.

  The production can also be carried out using an acidic ion exchange resin.

  This ion exchange can be carried out by the method disclosed in WO 03/76518.

  According to the invention, the mixtures according to the invention contain component (B) which likewise consists of an anionic boron compound of the formula (VII).

These anionic boron compounds have an x-valent positively charged cation Kat ⁺ as their counter ion. In this case this may be, for example, an alkali (earth) metal- or ammonium ion, such as Mg ²⁺ , Li ⁺ , Na ⁺ or K ⁺ , but ammonium ions are preferred.

An ammonium ion in the sense of the present invention is an ionic compound containing at least one nitrogen atom having several substituents, where the substituents are C ₁ -C ₁₈ -alkyl and C ₆ -C ₁₂ -aryl. An alkyl group is preferred. Of course, two or more substituents may be bonded to the ring, and the quaternary nitrogen atom may be a 5- to 6-membered ring portion.

  Examples of ammonium cations are tetra-n-octylammonium, tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, trimethylbenzylammonium, trimethylcetylammonium, triethylbenzylammonium, tri-n-butylbenzylammonium, trimethylethyl. Ammonium, tri-n-butylethylammonium, triethylmethylammonium, tri-n-butylmethylammonium, di-isopropyl-diethylammonium, di-isopropyl-ethylmethylammonium, di-isopropyl-ethyl-benzylammonium, N, N- Dimethylpiperidinium, N, N-dimethylmorpholinium, N, N-dimethylpiperazinium or N-methyl-diazabisch [2,2,2] octane. Preferred alkylammonium ions are tetraoctylammonium, tetramethylammonium, tetraethylammonium and tetra-n-butylammonium, particularly preferably tetraoctylammonium and tetra-n-butylammonium, with tetra-n-butylammonium being particularly preferred. .

  Ammonium ions containing a ring system are, for example, methylated, ethylated, n-butylated, cetylated or benzylated piperazine, piperidine, imidazole, morpholine, quinuclidine, cinnoline, pyridine or triethylenediamine.

The mixture according to the invention is
At least one component (A) of formula 1 / m An ^m- Cya ⁺ as described above and preferably at least one component (B) of formula (VII) (having counterion 1 / x Kat ^{x +} ) Contains.

The mixtures according to the invention can be used as component (B) instead of or in addition to an anionic boron compound of the formula (VII) having its counterion 1 / x Kat ^{x +} , sulfonium salts, iodonium salts, sulfones, peroxides, pyridines It can also contain -N-oxide or halogen methyltriazine.

  Suitable sulfonium salts are described, for example, in DE-A1 19730498, in particular on page 3, line 28-39, and the invention will become clear by reference to this description.

［式中、Ｒ^１８及びＲ^１９は、それぞれ置換又は非置換のアリール基を表し、Ｒ^２０は置換又は非置換のアルキル基、置換又は非置換のアルケニル基、置換又は非置換の環状脂肪族基、置換又は非置換のアリール基又は置換又は非置換のアラルキル基を表し、ＡｎＡ⁻はアニオンを表す］のものが有利である。 In this case, the salt has the formula:

[Wherein R ¹⁸ and R ¹⁹ each represent a substituted or unsubstituted aryl group, and R ²⁰ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cyclic aliphatic group. represents a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group, AnA ^- is advantageously that of an anion.

  Triphenylsulfonium, diphenylanisylsulfonium, diphenyl- (4-tolyl) -sulfonium, diphenyl- (4-fluorophenyl) -sulfonium, diphenyl- [4- (phenylthio) -phenyl) -sulfonium, diphenylbenzylsulfonium, diphenyl- (4-chlorobenzyl) -sulfonium, diphenyl- (4-bromobenzyl) sulfonium, diphenyl- (4-cyanobenzyl) -sulfonium, di- (4-tert-butylphenyl) -benzylsulfonium, dianisyl (4-bromophenyl) Sulfonium, diphenylphenacylsulfonium, diphenyl- (4-chlorophenacyl) sulfonium, diphenyl- (4-cyanophenacyl) -sulfonium, diphenylallylsulfonium, dipheni Mesyl sulfonium, diphenyl -p- toluenesulfonyl methyl sulfonium, diphenyl - (dimethyl sulfonium methyl) - sulfonium and diphenyl - [4- (diphenyl sulfonium yl) - phenyl] - sulfonium are particularly preferred.

Preferred anions AnA ⁻ are BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , Cl ⁻ , Br ⁻ , tetraphenylborate, tetrakis- (pentafluorophenyl) -borate, benzenesulfonate anion, p-toluenesulfonate anion and trifluoromethanesulfonate anion.

  Suitable iodonium salts are described, for example, in DE-A1 19730498, in particular on page 3, line 40-43, and the invention will become apparent by reference to the description.

In this case, the formula:
R ²¹ −I ⁺ −R ²² AnB ⁻
[Wherein R ²¹ and R ²² represent a substituted or unsubstituted aryl group, and AnB ⁻ represents an anion] are preferred.

  Particular preference is given to diphenyliodonium, anisylphenyliodonium, di- (4-tert-butylphenyl) -iodonium, di- (4-chlorophenyl) -iodonium, di-tolyliodonium and di (3-nitrophenyl) -iodonium.

Preferred anions AnB ⁻ are BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , Cl ⁻ , Br ⁻ , tetraphenylborate, tetrakis- (pentafluorophenyl) -borate, benzenesulfonate anion, p-toluenesulfonate anion and trifluoromethanesulfonate anion.

  Suitable sulfones are described, for example, in DE-A1 19730498, in particular on page 4, line 1-12, and the invention will become apparent by reference to the description.

［式中、Ｒ^２３は置換又は非置換のアリール基を表し、基Ｒ^２４はそれぞれハロゲン原子を表す］のものが好ましい。 Where the formula:

[Wherein R ²³ represents a substituted or unsubstituted aryl group, and each group R ²⁴ represents a halogen atom] is preferred.

  Within the scope of this specification halogen includes fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, particularly preferably chlorine.

  Trichloromethylphenylsulfone, tribromomethylphenylsulfone, trichloromethyl-4-chlorophenylsulfone, tribromomethyl-4-nitrophenylsulfone, 2-trichloromethylbenzothiazolesulfone, 2,4-dichlorophenyltrichloromethylsulfone, 2-methyl- 4-chlorophenyltrichloromethylsulfone and 2,4-dichlorophenyltribromomethylsulfone are particularly preferred.

  Suitable peroxides are described, for example, in DE-A1 1974498, in particular on page 4, line 13-24, and the invention will become apparent by reference to the description.

［式中、Ｒ^２５は置換又は非置換のアリール基を表し、
Ｒ^２６は置換又は非置換のアルキル基、置換又は非置換のアリール基又は置換又は非置換のベンゾイル基、好ましくは式−Ｒ^２５−（ＣＯ）−を表す］のものが好ましい。 formula:

[Wherein R ²⁵ represents a substituted or unsubstituted aryl group,
R ²⁶ is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzoyl group, preferably of the formula —R ²⁵ — (CO) —.

  Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, di- (t-butylperoxy) -isophthalate, di- (t-butylperoxy) -terephthalate, di- (t-butylperoxy) -phthalate 2,5-dimethyl-di- (benzoylperoxy) -hexane and 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) -benzophenone are particularly preferred.

  Suitable pyridine-N-oxides are described, for example, in DE-A1 19730498, in particular on page 3, line 44-62, and the invention will become apparent by reference to the description.

［式中、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３０又はＲ^３１はそれぞれ相互に無関係に、水素原子、ハロゲン原子、シアノ基、置換又は非置換のアルキル基、置換又は非置換のアルコキシ基又は置換又は非置換のアリール基を表し、Ｒ^３２は、置換又は非置換のアルキル基を表し、ＡｎＣ⁻はアニオンを表す］のものが好ましい。 In this case, the formula:

[Wherein, R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ or R ³¹ independently represent a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or It preferably represents a substituted or unsubstituted aryl group, R ³² represents a substituted or unsubstituted alkyl group, and AnC ⁻ represents an anion].

  N-methoxypyridinium, N-ethoxypyridinium, N-methoxy-2-picolinium, N-methoxy-3-picolinium, N-ethoxy-2-picolinium, N-ethoxy-3-picolinium, N-methoxy-4-bromopyridinium N-methoxy-3-bromopyridinium, N-methoxy-2-bromopyridinium, N-ethoxy-4-bromopyridinium, N-ethoxy-3-bromopyridinium, N-ethoxy-2-bromopyridinium, N-ethoxy- 4-chloropyridinium, N-ethoxy-3-chloropyridinium, N-ethoxy-2-chloropyridinium, N-methoxy-4-methoxypyridinium, N-methoxy-3-methoxypyridinium, N-methoxy-2-methoxypyridinium, N-Ethoxy-4-methoxy Pyridinium, N-ethoxy-3-methoxypyridinium, N-ethoxy-2-methoxypyridinium, N-methoxy-4-phenylpyridinium, N-methoxy-3-phenylpyridinium, N-methoxy-2-phenylpyridinium, N-ethoxy -4-phenylpyridinium, N-ethoxy-3-phenyl-pyridinium, N-ethoxy-2-phenylpyridinium, N-methoxy-4-cyanopyridinium, N-ethoxy-4-cyanopyridinium, N, N'-dimethoxy- Particularly, 4,4′-bipyridinium, N, N′-diethoxy-4,4′-bipyridinium, N, N′-dimethoxy-2,2′-bipyridinium and N, N′-diethoxy-2,2′-bipyridinium preferable.

Preferred anions AnC ⁻ are BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , Cl ⁻ , Br ⁻ , tetraphenylborate, tetrakis- (pentafluorophenyl) -borate, benzenesulfonate anion, p-toluenesulfonate anion and trifluoromethanesulfonate anion.

  Suitable halogenmethyltriazines are described, for example, in DE-A1 19730498, in particular on page 4, line 25-40, the invention will become apparent by reference to the description.

［式中、Ｒ^３３、Ｒ^３４及びＲ^３５はそれぞれ相互に無関係に、トリハロゲンメチル基、置換又は非置換のアルキル基、置換又は非置換のアルケニル基又は置換又は非置換のアリール基を表す、但し、基の少なくとも１個はトリハロゲンメチル基であることを条件とする］のものが有利である。 In this case, the formula:

[Wherein, R ³³ , R ³⁴ and R ³⁵ independently represent a trihalogen methyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group or a substituted or unsubstituted aryl group, Provided that at least one of the groups is a trihalogenmethyl group).

  2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2,4-bis- (dichloromethyl) -6-trichloromethyl-s -Triazine, 2-propionyl-4,6-bis- (trichloromethyl) -s-triazine, 2-benzoyl-4,6-bis- (trichloromethyl) -s-triazine, 2- (4-cyanophenyl-4 , 6-Bis- (trichloromethyl) -s-triazine, 2- (4-nitrophenyl) -4,6-bis- (trichloromethyl) -s-triazine, 2- (4-chlorophenyl-4,6-bis -(Trichloromethyl) -s-triazine, 2- (4-cumenyl) -4,6-bis- (trichloromethyl) -s-triazine, 2- (4-aminophenyl) -4,6 Bis- (trichloromethyl) -s-triazine, 2,4-bis- (4-methoxyphenyl) -6-trichloromethyl, 2,4-bis- (3-chlorophenyl) -6-trichloromethyl-s-triazine, 2- (4-methoxystyryl (trichloromethyl) -s-triazine, 2- (4-chlorostyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-aminophenyl)- 4,6-bis- (trichloromethyl) -s-triazine, 2,4-bis- (4-methoxyphenyl) -6-trichloromethyl-s-triazine, 2,4-bis- (3-chlorophenyl) -6 Trichloromethyl-s-triazine, 2- (4-methoxystyryl) -4,6-bis- (trichloromethyl) -s-triazine, 2- (4-chlorostyryl) ) -4,6-bis- (trichloromethyl) -s-triazine, 2- (4-aminostyryl) -4,6-bis- (dichloromethyl) -s-triazine, 2- (4′-methoxy-1) '-Naphtyl) -4,6-bis- (trichloromethyl) -s-triazine and 2- (6'-nitro-1'-naphthyl) -4,6-bis- (trichloromethyl) -s-triazine are special preferable.

  Furthermore, this mixture can still contain at least one solvent (C). This may be, for example: esters such as butyl acetate or ethyl acetate, aromatic or (cyclo) aliphatic hydrocarbons such as xylene, toluene or heptane, ketones such as acetone, iso-butyl methyl ketone, Methyl ethyl ketone or cyclohexanone, alcohols such as ethanol, isopropanol, mono- or lower oligoethylene- or -propylene glycol, 1- or 2-etherified ethylene- or propylene glycol ethers, glycol ether acetates such as methoxypropyl acetate, cyclic Ethers such as tetrahydrofuran, carboxylic acid amides such as dimethylformamide or N-methylpyrrolidone and / or water.

Preferred mixtures of the present invention are:
-At least one component (A) of the formula 1 / m An ^m- Cya ⁺ as described above,
-Preferably component (B) of formula (VII) (having counterion 1 / x Kat ^{x +} ) less
Both are at least one type and optionally at least one type of solvent (C).

  In a preferred embodiment, the mixtures according to the invention can be used without solvent (C).

In the mixture according to the invention, the weight ratio between component (A) of formula 1 / m An ^m- Cya ⁺ and component (B) of formula (VII) having counter ion 1 / x Kat ^{x +} is preferably 1: 1
˜1: 5, particularly preferably 1: 1 to 1: 4, very particularly preferably 1: 2 to 1: 4.

The mixture according to the invention is well soluble in the coating composition. This solubility can be affected by the choice of anion and the choice of substituents on the cation. Long alkyl chains as groups R ¹⁰ , R ¹¹ or R ¹² or as substituents on cyanine generally also result in improved solubility.

  The sensitizing dye according to the present invention usually exhibits maximum absorption in the wavelength range of 700 nm to 1200 nm. This maximum absorption of the sensitizing dye can be influenced by the choice of substituents on the cyanine cation in a manner known in principle by those skilled in the art.

  The NIR-line used for photocuring may be broad radiation from photodiodes (LEDs), halogen lamps, Xe-lamps and the like. This may be narrow-width radiation or a laser beam with a specific wavelength. As the laser, lasers generated in the NIR range, for example semiconductor diode lasers, are particularly suitable. The radiation can be delivered continuously or as pulses, for example in the form of a flash.

  Another object of the invention is a radiation curable coating composition containing the mixture according to the invention.

Such coating compositions typically contain the following:
-At least one component (A) of formula 1 / m An ^m- Cya ⁺ as described above-and preferably less component (B) of formula (VII) having the counter ion 1 / x Kat ^{x +}
1 type
-Optionally at least one solvent (C),
-At least one binder (D),
-Optionally at least one reactive diluent (E),
-Optionally at least one UV-photoinitiator (F),
-Optionally at least one colorant (G) and-optionally other typical paint additives (H).

  The binder (D) is a compound having an ethylenically unsaturated group capable of radical or cationic polymerization. This radiation curable composition comprises 0.001-12 radiation curable ethylenically unsaturated groups, particularly preferably 0.1-8, particularly preferably 0.5-7 moles per 1000 g of radiation curable compound. It is advantageous to contain.

  Examples of radiation curable compounds are (meth) acrylic compounds, vinyl ethers, vinyl amides, such as unsaturated polyesters based on maleic acid or fumaric acid or maleimide / vinyl ether systems.

  (Meth) acrylate compounds such as polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, carbonate (meth) acrylate, silicon (meth) acrylate, acrylated polyacrylate Is preferred.

  Advantageously, at least 40 mol%, particularly preferably at least 60%, of the radiation curable ethylenically unsaturated groups are (meth) acrylic groups.

  The radiation curable compound can be present, for example, as a solution in an organic solvent or water, as an aqueous dispersion, or as a powder.

  Also preferred are radiation curable compounds and thus radiation curable compositions that are flowable at room temperature. However, it may also be advantageous to apply the radiation curable compound or coating composition in the form of a melt or as a powder (powder paint). The radiation curable composition preferably contains less than 20% by weight, in particular less than 10% by weight of organic solvent and / or water. Solvent-free and water-free (so-called 100% system) are preferred. In this case, the drying step can be advantageously omitted.

  The reactive diluent (E) is, for example, an ester of (meth) acrylic acid and an alcohol having 1 to 20 carbon atoms, such as (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth). Acrylic acid butyl ester, (meth) acrylic acid-2-ethylhexyl ester, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, dihydrodicyclopentadienyl acrylate, vinyl aromatic compounds such as styrene, divinylbenzene, α, β Unsaturated nitriles such as acrylonitrile, methacrylonitrile, α, β-unsaturated aldehydes such as acrolein, methacrolein, vinyl esters such as vinyl acetate, vinyl propionate, halogenated ethylenically unsaturated compounds such as vinyl chloride , PVC Ridene, conjugated unsaturated compounds such as butadiene, isoprene, chloroprene, monounsaturated compounds such as ethylene, propylene, 1-butene, 2-butene, iso-butene, cyclic monounsaturated compounds such as cyclopentene, cyclohexene, cyclododecene, N -Vinylformamide, allyl acetic acid, vinyl acetic acid, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and their water-soluble alkali metal-, alkaline earth metal- or ammonium salts such as acrylic acid, methacrylic acid Dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylene malonic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid, N-vinyl pyrrolidone, N-vinyl lactam such as N-vinyl caprolactam, N-vinyl- N-alkyl-ca Rubonic acid amides or N-vinyl-carboxylic acid amides such as N-vinylacetamide, N-vinyl-N-methylformamide and N-vinyl-N-methylacetamide or vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether N-butyl vinyl ether, s-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 4-hydroxybutyl vinyl ether, and mixtures thereof.

  In this specification (meth) acrylic acid means methacrylic acid and acrylic acid, preferably acrylic acid.

  UV-photoinitiators (F) include photoinitiators known to those skilled in the art, such as "Advances in Polymer Science", Vol. 14, Springer Berlin 1974 or KK Dietliker, Chemistry and Technology of UV-and EB-Formulation for Coatings, Inks and Paints, Vol.3; Photo-initiators for Free Radical and Cationic Polymerization, PKTOldring (Eds), SITA Technology Ltd. London can be used. Contrary to NIR-photoinitiators, UV-photoinitiators are essentially light in the wavelength range of λ = 200-700 nm, particularly preferably λ = 200-500 nm, very particularly preferably λ = 250-400 nm. Excited.

  According to the invention, this is understood to be a photoinitiator that releases radicals under the action of light and can initiate radical reactions, for example radical polymerization.

  This includes, for example, phosphine oxide, benzophenone, α-hydroxy-alkyl-aryl-ketones, thioxanthone, anthraquinone, acetophenone, benzoin and benzoin-ether, ketals, imidazoles or phenylglyoxylic acid and mixtures thereof.

Phosphine oxides are, for example, mono- or bisacylphosphine oxides such as those described in EP-A 7508, EP-A 57474, DE-A 19618720, EP-A 495751 or EP-A 615980, for example 2,4,6-trimethylbenzoyldiphenyl. Phosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate or bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide,
Examples of benzophenone include benzophenone, 4-aminobenzophenone, 4,4′-bis (di-methylamino) benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Michler's ketone, o-methoxybenzophenone, 2,4,6-trimethylbenzophenone. 4-methylbenzophenone, 2,4-dimethylbenzophenone, 4-isopropylbenzophenone, 2-chlorobenzophenone, 2,2′-dichlorobenzophenone, 4-methoxybenzophenone, 4-propoxybenzophenone or 4-butoxybenzophenone,
α-Hydroxy-alkyl-aryl-ketones are, for example, 1-benzoylcyclohexane-1-ol (1-hydroxy-cyclohexyl-phenyl ketone), 2-hydroxy-2,2′-dimethylacetophenone (2-hydroxy-2-methyl). -1-phenyl-propan-1-one), 1-hydroxyacetophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one or 2- A polymer containing hydroxy-2-methyl-1- (4-isopropen-2-yl-phenyl) -propan-1-one for polymerization introduction,
Xanthone and thioxanthone are, for example, 10-thioxanthenone, thioxanthen-9-one, xanthen-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di-isopropylthioxanthone, 2, 4-dichlorothioxanthone or chloroxanthenone,
Anthraquinones are, for example, β-methylanthraquinone, t-butylanthraquinone, anthraquinone carboxylic acid ester, benz [de] anthracene-7-one, benz [a] anthracene-7,12-dione, 2-methylanthraquinone, 2-ethylanthraquinone. , 2-t-butylanthraquinone, 1-chloroanthraquinone or 2-amylanthraquinone,
Examples of acetophenone include acetophenone, acetonaphthoquinone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, p-diacetylbenzene, 4′-methoxyacetophenone, α-tetralone. 9-acetylphenanthrene, 2-acetylphenanthrene, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, 1,3,4-triacetylbenzene, 1-acetonaphthone, 2 -Acetonaphthone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 2,2-diethoxyacetate Phenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-2-one or 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butan-1-one;
Benzoin or benzoin ether is, for example, 4-morpholinodeoxybenzoin, benzoin, benzoin-isobutyl ether, benzoin-tetrahydropyranyl ether, benzoin-methyl ether, benzoin-ethyl ether, benzoin-butyl ether, benzoin-isopropyl ether or 7-H-benzoin -Methyl ether or ketal is, for example, acetophenone dimethyl ketal, 2,2-diethoxyacetophenone or benzyl ketal, for example benzyl dimethyl ketal.

  Phenylglyoxylic acid is described, for example, in DE-A 198 26 712, DE-A 19133353 or WO 98/33761.

  Further usable photoinitiators are, for example, benzaldehyde, methyl ethyl ketone, 1-naphthaldehyde, triphenylphosphine, tri-o-tolylphosphine or 2,3-butanedione.

  Typical mixtures include, for example, 2-hydroxy-2-methyl-1-phenyl-propan-2-one and 1-hydroxy-cyclohexyl-phenyl ketone, bis (2,6-dimethoxybenzoyl) -2,4,4. Trimethyl-pentylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzophenone and 1-hydroxy-cyclohexyl-phenylketone, bis (2,6-dimethoxybenzoyl) -2,4 4-trimethylpentyl-phosphine oxide and 1-hydroxy-cyclohexyl-phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2, 4,6-trimethylbenzophenone and 4-methylbenzene Zofenon or 2,4,6-trimethyl benzophenone and 4-methylbenzophenone and 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and the like.

  In a preferred embodiment of the invention, at least one UV-photoinitiator is present in the coating composition according to the invention.

  Throughout this specification the colorant (G) means pigments and dyes, preferably pigments.

  Pigment (G) is a particulate “substantially insoluble in the medium used, inorganic or organic, according to the instructions of DIN55943 in CD Roempp Chemie Lexikon-Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995. A chromatic or achromatic colorant.

  “Substantially insoluble” in this case means that the solubility at 25 ° C. is less than 1 g / 1000 g of medium used, preferably less than 0.5, particularly preferably less than 0.25, very particularly preferably less than 0. Means less than 1, in particular less than 0.05 g / 1000 g of medium used.

  Examples of pigments in the specific sense include any system of absorbing and / or effect pigments, preferably absorbing pigments. In this case, the listing and selection of pigment components is in no way limiting. These can be arbitrarily adapted to the respective needs, for example the desired color impression. For example, all pigment components can be the basis for a standardized mixed paint system.

Effect pigments are to be understood as all pigments which exhibit a lamellar structure and provide a special decorative color effect for the surface coating. The effect pigments are all pigments that give an effect that can normally be used, for example, in vehicles and in industrial coatings. Examples of such effect pigments are pure metal pigments; for example, aluminum-, iron- or copper pigments; interference pigments, for example titanium dioxide-coated mica, iron oxide-coated mica, mixed oxides (for example titanium dioxide and Mica coated with Fe ₂ O ₃ or titanium dioxide and Cr ₂ O ₃ ), metal oxide coated aluminum or liquid crystal pigment.

  The chromatic absorbing pigment is, for example, an organic or inorganic absorbing pigment that can be usually used in the paint industry. Examples of organic absorbing pigments are azo pigments, phthalocyanine-, quinacridone- and pyrrolopyrrole pigments. Examples of inorganic absorbing pigments are iron oxide pigments, titanium dioxide and carbon black.

  Dyes are also colorants, differing from pigments by their solubility in the use medium, i.e. they have a solubility in the use medium of more than 1 g / 1000 g at 25 [deg.] C.

  Examples of dyes are azo-, azine-, anthraquinone-, acridine-, cyanine-, oxazine-, polymethine-, thiazine-, triarylmethane-dyes. These dyes can be basic or cationic dyes, mordants-, direct-, disperse-, developed-, vat-dyes-, metal complexes-, reactive-, acid-, sulfur-, coupling- or direct dyes. Can be used.

  Other typical paint additives (H) include, for example, antioxidants, stabilizers, activators (accelerators), fillers, antistatic agents, flame retardants, thickeners, thixotropic agents, surfactants, Viscosity modifiers, plasticizers or chelating agents can be used.

  As thermal post-curing accelerators, for example, tin octoate, zinc octoate, dibutyltin laurate or diaza [2.2.2] bicyclooctane can be used.

  In addition, one or more photochemically and / or thermally activatable initiators such as potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-t-butyl peroxide, azobis-iso-butyronitrile, cyclohexylsulfonylacetyl peroxide , Di-iso-propyl percarbonate, t-butyl peroctoate or benzpinacol, and thermally activatable initiators such as e.g. di-t- Butyl peroxide, cumol hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, silylated pinacol (which is commercially available, for example, under the trade name ADDID 6000 from Firm Wacker) or hydroxyl group-containing amines - oxide, may be added for example 2,2,6,6-tetramethylpiperidine -N- oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine -N- oxyl like.

  Further examples of suitable initiators are described in "Polymer Handbook", 2. Aufl., Wiley & Sons, New York.

  As thickeners, conventional organic and inorganic thickeners such as hydroxymethylcellulose or bentonite are used alongside radical (co) polymerized (co) polymers.

  As a chelating agent, for example, ethylenediamineacetic acid and its salt and β-diketone can be used.

  Color-inactive fillers are on the one hand color-inactive; i.e. exhibit a low intrinsic absorption and have a refractive index similar to that of the coating medium, on the other hand in the surface coating, i.e. applied. It should be understood that all substances / compounds that can influence the orientation (parallel arrangement) of the effect pigments in the coated film and further affect the properties of the coating or coating composition, eg hardness or rheology. is there. The inert materials / compounds that can then be used are listed by way of example, but the concept of fillers affecting the color inert topology should not be limited to these examples alone. Suitable inert fillers corresponding to this definition may be, for example, transparent or translucent fillers or pigments, such as plastic granules, silica gel, Blancfix, diatomaceous earth, talc, calcium carbonate, chalk, kaolin. , Barium sulfate, magnesium silicate, aluminum silicate, crystalline silicon dioxide, amorphous silicic acid or aluminum oxide. In addition, any solid inert organic particles such as urea-formaldehyde condensation products, micronized polyolefin waxes and micronized amide waxes can be used as inert fillers. The inert fillers can also be used as a mixture. However, it is preferred to use only one filler each.

  Suitable stabilizers include typical UV-absorbers such as oxyanilide, triazine and benzotriazole and benzophenone. These may be used alone or as a suitable radical scavenger, such as sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-t-butylpyridine or their derivatives such as It can also be used with bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate. The stabilizer is usually used in an amount of 0.1 to 5.0% by mass with respect to the solid component contained in the composition.

  The mixtures according to the invention can be used as NIR-activatable photoinitiators and are better in coating compositions and paint systems than the formulations known from the state of the art of NIR-photoinitiators. In this case, the borate ion of the formula (VII) functions as a counterion for the cyanine cation. This, on the one hand, allows the photoinitiator to be uniformly dispersed in the paint system and does not leave insoluble particles as defects in the subsequent paint, while producing high photoreactivity. Result. In the NIR-photoinitiators known from the state of the art, the compound precipitates as crystals in the coating composition as crystals based on partial lack of solubility.

  In order to obtain this improved solubility, the mixtures according to the invention are prepared by means of radiation curable compounds, ie binders (D) and / or reactive diluents (E) or compositions containing them, for example coating compositions. , Mixed with paint or paint formulation.

In another embodiment of the invention, the radiation curable compound of the component (A) of formula 1 / m An ^m- Cya ⁺ as defined above, optionally diluted in a solvent, It can be mixed with at least one component (B) of formula (VII) having at least one and, alternatively, a counterion 1 / x Kat ^{x +} , optionally diluted in a solvent.

  In this case, it is not important how the mixing is performed according to the present invention. For example, this can be achieved by using mechanical stirrers, such as discs, inclined plates, anchors, strong- or gas-dispersed stirrers, by circulation, optionally through slit blinds or in mixer pumps, or often by two-component hands Alternatively, it can be carried out by simple mixing by vibration. Of course, mixing techniques using high shear energy such as jet dispersion, high power, Ultraturrax, or ultrasonic dispersion can also be used.

  It is a special advantage of NIR-photoinitiators that such photoinitiators can initiate radical polymerization even in pigmented paints. That is to say that the UV radiation which is necessary for the activation of the UV-photoinitiator, ie that the activating radiation is usually not absorbed or only slightly absorbed by the pigment. Is usually absorbed and / or diffused by the pigment and thus exhibits a slight penetration depth into the coating. Therefore, the use of the mixture according to the invention in a pigmented coating composition is a preferred embodiment of the invention.

  Another advantageous embodiment of the invention consists in using the mixture according to the invention in a coating composition having a high layer thickness. It is a preferred embodiment that the mixture is used in a coating composition having a layer thickness of more than 30 μm, preferably more than 45, particularly preferably more than 60 μm. The coating composition can have a thickness of up to 300, preferably up to 250, particularly preferably up to 200 μm.

  Of course, the coating can be thicker or thinner, for example 10 to 1000 μm. However, for very thickly applied coating compositions, it may be necessary to irradiate several times.

  The radiation curable coating composition is preferably applied in a simple manner, e.g. spraying, troweling, brushing, doctor, brush, rolling, roller coating, flow coating, dipping, laminating, injection-butt molding (Hinterspritzen ) Or co-extrudieren or the like and can be applied to the object to be coated and optionally dried.

  For curing, irradiation is carried out with visible NIR-range, preferably with electromagnetic radiation including the NIR-range, particularly preferably with electromagnetic radiation with a wavelength of 700-900 nm.

  This irradiation can also be carried out in the absence of oxygen in one preferred embodiment of the invention. For this purpose, irradiation is carried out so that the coating composition is exposed to an oxygen partial pressure below 18 kPa at the moment of irradiation with NIR-rays. An important range is the surface area with the radiation curable coating composition of the object to be coated at the moment of exposure. The oxygen partial pressure is preferably below 17 kPa, particularly preferably below 15.3 kPa, very particularly preferably below 13.5 kPa, in particular below 10 kPa, in particular below 6.3 kPa.

  Often, the complete absence of oxygen is not necessarily required, so the oxygen partial pressure is preferably not more than 0.5 kPa, particularly preferably 0.9 kPa, very particularly preferably 1.8 kPa, in particular 2.5 kPa.

  For example, improved scratch strength is advantageously observed by curing at low oxygen partial pressures.

  Such a low oxygen partial pressure is preferably effected by dilution of the oxygen-containing atmosphere with at least one inert gas or by replacement with at least one inert gas, ie a gas that does not react under radiation curing conditions. be able to. As the inert gas, nitrogen, rare gas, carbon dioxide or fuel gas is particularly suitable. In the atmosphere in which the radiation curing is carried out, the proportion of the at least one inert gas is more than 80% by volume, preferably at least 85, particularly preferably at least 90, very particularly preferably at least 95, in particular It should be at least 98% by volume. Furthermore, irradiation can be performed by a method of covering the coating composition with a transparent medium. Transparent media are, for example, plastic sheets, glass and liquids, such as water. This irradiation is particularly preferably carried out as described in WO 01/14483, which can be referred to. Irradiation in the manner as described in DE-A1 1995757900 is quite particularly advantageous, which can be referred to.

  The coating compositions and paint formulations according to the invention can be used in particular for substrates such as wood, preferably pine, spruce, beech, oak or maple wood, paper, cardboard, paperboard, textile materials, leather, substitute leather, Fleece, plastic surface, preferably SAN, PMMA, ABS, PP, PS, PC or PA (abbreviated according to DIN 7728), glass, ceramic, inorganic building materials such as cement-molded stone and fiber cement plates or metal or coated For example, it is suitable for coatings of plastics or metals which can also be present as sheets, for example. In this case, the metal or coated metal may be formed into a roll, for example a so-called coil, for storage or transport. This metal coating can contain the usual primer coating (primer) or cathodic dipping coating.

  The coating composition according to the invention is particularly suitable for outdoor painting or for painting indoors, vehicles or airplanes, preferably in building or building component applications as exposed to daylight. is there. In particular, the coating compositions according to the invention are used as or in automotive clearing and overcoat lacquers and in paints, in particular outdoor paints, industrial paints, coil coatings, moldings, castings or dentals. Used in industrial compounds. Furthermore, the mixtures according to the invention can be used for curing building materials, bricks, clinker, artificial stone, striking floors, plaster and coating compositions for their coating. Advantageously, the coating composition according to the invention can be used for furniture-, parquet floor-, laminate- and flooring, especially for decorative painting.

  Furthermore, the coating composition according to the invention can be used in printing processes or for the production of printing plates, for example in stereolithography, photographic lithography, screen printing, offset, lithographic printing, intaglio printing, or letterpress printing. In addition, the ink jet method (Ink-Jet) can be used.

  The characteristics of the present invention will be described in the following examples, but the present invention is not limited thereto.

  “Part” or “%” in this specification is “part by mass” or “% by mass” unless otherwise specified.

  Synthetic NIR-sensitizers A1-A10 according to the present invention are summarized in Table 1. As comparative examples, NIR dyes (B1 to B10) not according to the invention in the form of corresponding iodides are used.

  The NIR-absorbent according to the invention can be synthesized in a two-step process. In the first step, a cyanine-cation having a normal anion, such as iodide, is synthesized. This synthesis is in principle known to the person skilled in the art and can be carried out by synthesis known from the literature, for example K. Venkataraman "The Chemistry of Synthetic Dyes", Academic Press, New York, 1952, Bd. II and H. Zollinger “Color Chemistry: Synthesis, Properties, and Applications of Organic Dyes and Pigments”, Weinheim, Wiley-VCH, 2003.

  In the second step, the normal anion is exchanged with the anion according to the invention.

EXAMPLE A series of NIR-sensitizers according to the invention with improved solubility were synthesized.

First Step: Synthesis of Cyanine-Cation Having Normal Anion The following is an absorbent 2- [2- [2- [2- (1,3-dihydro-1-ethyl-3,3-dimethyl-2H-indole] 2-ylidene) -ethylidene] -1-cyclohexen-1-yl] ethenyl] -1-ethyl-3,3-dimethyl-3H-indolium iodide (B1) is exemplified.

  10 g (0.032 mol) of 3-ethyl-1,1,2-trimethylindolium iodide and 2.7 g (0.016 mol) of 3-hydroxymethylene-cyclohex-1-ene-carbaldehyde were added to 105 ml of butanol and Charged into a mixture from 45 ml of toluene. This was heated to 110 ° C. and the resulting water was removed from the system. After stirring for 5 hours, it was allowed to cool to room temperature. After concentration of the solution, methyl-t-butyl ether was added. The resulting crystals were filtered off with suction and washed with methyl-t-butyl ether. 9.4 g of crystals were obtained and dried in vacuo at 50 ° C. (melting point 235 ° C.).

  Other cyanine-cations with the usual anions were synthesized using the corresponding starting compounds in a similar manner.

Second Step: General Formula for Producing NIR-Sensitizers According to the Present Invention by Exchange of Anions 2- [2- [2- [2- (1,3-Dihydro-1-ethyl-3,3-dimethyl- 2H-indole-2-ylidene) -ethylidene] -1-cyclohexen-1-yl] ethenyl] -1-ethyl-3,3-dimethyl-3H-indolium dodecylsulfonate (A1)
The compound was prepared as follows: NIR-sensitizer A1 0.003 mol (1.6 g) was precharged in 50 ml dichloromethane together with 0.009 mol (2.3 g) Na-dodecylsulfonate. did. 50 ml of water was added and stirred for 30 minutes at room temperature and finally the phases were separated. The organic phase was washed 3 times with 50 ml of water until iodine could no longer be detected with the silver nitrate solution in the wash water. After drying the organic phase with sodium sulfate, the solvent was distilled off and the residue was dried at 50 ° C. in vacuo.

  In a similar manner, the following NIR-sensitizers were prepared using other cyanine-cations as well as the corresponding salts of the desired anion. The synthesized NIR-sensitizers according to the invention are summarized in Table 1.

  For comparison purposes, a series of NIR-sensitizers (iodide-salts similar to A1-A10) not according to the invention were used.

Co-initiator X used:

Comparison of solubility of NIR-sensitizer in paint raw materials:
For this test, were used conventional radical polymerizable coating material two acrylate type ^{(Laromer (R)} LR8863 and Laromer ^(R) LRPO84F, both BASF AG).

  A specified amount of NIR-sensitizer was added to each, and stirred at room temperature for at least 4 hours. Using polarization microscopy, it was examined whether the resulting liquid still contained insoluble crystals of NIR-sensitizer.

  NIR-sensitizers B7, B11 and B12 not according to the invention were unsatisfactorily soluble in both solutions (solubility <0.1% by weight respectively).

  On the other hand, with NIR-sensitizers A7, A11 and A12 according to the present invention, a clear solution having no insoluble crystals was obtained even with 0.5% by mass of each corresponding NIR-sensitizer.

Test of NIR-sensitizer in photoinitiator mixture:
NIR-sensitizer 0.5% by mass and borate salt X ^- 1.5% by mass were added to both of the paint raw materials, respectively, and the mixture was vigorously stirred. A thin layer (layer thickness: about 50 μm) was produced between the two glass plates having the spacer sheet by using the obtained mixture. These layers were exposed to a 250 W halogen lamp (interval of about 15 cm) for 1 minute.

Comparative example:
NIR-sensitizers B7, B11, and B12 not according to the present invention were not completely dissolved in the coating material. A coating that was not completely cured after exposure was obtained. Further, colored spots (crystals not dissolved under a polarizing microscope) were present in the paint.

Example:
The NIR-sensitizers A7, A11 and A12 according to the present invention were completely dissolved in the coating material. Already after an exposure time of 4 seconds, a hard and clear coating was obtained without spots.

Claims (12)

The following components (A) and (B):
(A) Sensitizer composed of at least one cyanine-cation Cya ⁺ and corresponding anion 1 / m An ^m- at least one {in this case, the cyanine-cation is represented by the general formula (I), (II ), (III) or (IV):

[Wherein n is 1 or 2 and the groups R ^{1 to} R ⁹ are:
R ¹ and R ² independently of one another are linear or branched, alkyl- or aralkyl groups having 1 to 20 carbon atoms,
R ³ and R ⁴ are H,
-R ⁵ and R ⁶ are independently of each other -H, -F, -Cl, -Br, -I, -NO ₂ ,
One or more substituents selected from the group consisting of —CN, —CF ₃ , —SO ₂ CF ₃ , —R ¹ , —OR ¹ , aryl- or —O-aryl,
- R ⁷ is, -H, -Cl, -Br, -I, - phenyl, -O- phenyl, -S- phenyl-, -N _{(phenyl) 2,} - pyridyl,
R ⁸ and R ⁹ are independent of each other> C (CH ₃ ) ₂ , —O—, —S—,> NR ¹ or —CH═CH—
Represents],
In this case, the anion An ^m- is represented by the formula:
[AR ¹⁰ _k ] ^m-
[Wherein k = 1, R ¹⁰ = -aryl-R ¹¹ , wherein R ¹¹ is a linear or branched alkyl group having 3 to 30 C atoms.
A is selected from the group consisting of —SO ₃ ⁻ , —OSO ₃ ⁻ , —COO ⁻ , —PO ₃ ²⁻ , —OPO ₃ ²⁻ or (—O) PO ₂ ^— .
In this case, in the groups R ¹⁰ and R ¹¹ , the non-adjacent C-atom may be substituted with an O-atom]} at least one and (B) alkyl-substituted as a co-initiator At least one borate salt,
A mixture containing The following ingredients:
At least one component (A) of the formula 1 / m An ^m- Cya ⁺ as defined in claim 1;
A mixture comprising at least one alkyl-substituted borate salt as co-initiator (B) and at least one solvent (C). The following ingredients:
At least one component (A) of the formula 1 / m An ^m- Cya ⁺ as defined in claim 1;
At least one alkyl-substituted borate salt as co-initiator (B),
-At least one solvent (C),
-At least one binder (D),
-At least one reactive diluent (E),
-At least one UV-photoinitiator (F),
-At least one colorant (G) and-other typical paint additives (H)
A coating composition containing The co-initiator (B) has one associated counter ion 1 / x Kat ^{x +} ,
Formula (VII):

[Wherein x is 1 or 2, Kat is an x-valent cation,
z ¹ , z ² , z ³ and z ⁴ are each independently 0 or 1,
Here, the sum of z ¹ + z ² + z ³ + z ⁴ is 0, 1, 2, or 3,
Y ¹ , Y ² , Y ³ and Y ⁴ are each independently O, S or NR ¹⁷ ;
R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently of each other interrupted by C ₁ -C ₁₈ -alkyl, one or more oxygen- and / or sulfur atoms and / or by one or more imino groups. C ₂ -C ₁₈ -alkyl, C ₆ -C ₁₂ -aryl, C ₅ -C ₁₂ -cycloalkyl or a 5- to 6-membered heterocycle having oxygen-, nitrogen- and / or sulfur atoms Wherein each of the groups described may be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, and R ¹⁷ is hydrogen, C ₁ -C ₁₈ -alkyl or C ₆ -C ₁₂ - aryl,
Provided that at least one of the groups R ^{13 to} R ¹⁶ is a C _{1 to} C ₁₈ -alkyl group;
At least one of the groups R ^{13 to} R ¹⁶ is a C _{6 to} C ₁₂ -aryl group, wherein the groups described are each aryl, alkyl, aryloxy, alkyloxy, heteroatom and / or heterocycle The mixture according to claim 1 or 2, or the coating composition according to claim 3, characterized in that the compound may be substituted by R ^{11 in} claim 1 is 1-propyl-, 2-propyl-, 1-butyl-, 2-butyl-, t-butyl-, 1-pentyl-, 1-hexyl-, cyclohexyl-, 2-ethyl. The method according to claim 1, characterized in that it is selected from the group consisting of -1-hexyl-, 1-octyl-, 1-nonyl, 1-decyl-, 1-undecyl-, 1-dodecyl- and 1-tetradecyl groups. A mixture according to claim 1 or 2 or a coating composition according to claim 3. The mixture according to claim 1 or 2, or the coating composition according to claim 3, characterized in that the anion An ^m- is a 4-alkylbenzenesulfonate having an alkyl group having 6 to 12 carbon atoms. . The anion An ^m- is selected from the group consisting of 4-hexylbenzenesulfonate, 4-octylbenzenesulfonate, 4-decylbenzenesulfonate and 4-dodecylbenzenesulfonate. Or a coating composition according to claim 3. The radiation curable coating composition, as well as building materials, brick, clinker, artificial stone, for curing the tapping floor or plaster, or coating compositions for these coatings, claims 1, 2, 4 Use of a mixture according to any one of the preceding 7. In a process for producing a radiation curable coating composition containing at least one binder (D) and / or reactive diluent (E), the binder (D) and / or reactive diluent (E) A process for producing a radiation curable coating composition, characterized in that it is mixed with the mixture according to any one of claims 1 , 2, 4 to 7 . In a process for producing a radiation curable coating composition containing at least one binder (D) and / or reactive diluent (E), the binder (D) and / or reactive diluent (E) Is mixed with at least one component (A) of the formula 1 / m An ^m- Cya ⁺ as defined in claim 1 and, alternatively, is alkyl-substituted as component (B) A method for producing a radiation curable coating composition, characterized in that it is mixed with at least one borate salt.   In a method of curing a coating composition comprising at least one mixture according to claim 1 and at least one radically polymerizable compound as a NIR-photoinitiator by irradiation with NIR-rays, this irradiation is carried out from 18 kPa. A process for curing a coating composition by irradiation with NIR-rays, characterized in that it is carried out under a low oxygen partial pressure.   The process according to claim 11, characterized in that the curing is carried out in an atmosphere containing at least one inert gas.